CN102039164B - Method for preparing adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst - Google Patents
Method for preparing adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst Download PDFInfo
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- CN102039164B CN102039164B CN2009102016465A CN200910201646A CN102039164B CN 102039164 B CN102039164 B CN 102039164B CN 2009102016465 A CN2009102016465 A CN 2009102016465A CN 200910201646 A CN200910201646 A CN 200910201646A CN 102039164 B CN102039164 B CN 102039164B
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Abstract
The invention relates to a method for preparing an adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst to mainly solve the following problems: the mordenite/beta zeolite symbiotic molecular sieves prepared in the prior art contain adhesives and have complex preparation processes and higher cost; the mordenite/beta zeolite symbiotic molecular sieve catalysts have lower activity when containing adhesives; the adhesive-free mordenite/beta zeolite molecular sieves have poorer strength; and the adhesive-containing mechanical mixture of mordenite and beta zeolite has lower activity. The invention preferably solves the above problems by adopting the following technical scheme: in terms of the weight of the catalyst after forming and roasting, mixing, forming and drying 10-80% of beta zeolite, 1-20% of alkaline substances, 1-20% of compounds of aluminium and 10-80% of silicon oxide, then putting the obtained mixture into steam containing at least one template agent from ammonia water, ethylene diamine, triethylamine, n-butylamine, hexamethylene diamine, tetrapropyl ammonium bromide or tetrapropyl ammonium hydroxide and crystallizing the mixture at the temperature of 120-200 DEG C for 10-240 hours to obtain the adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst. The adhesive-free mordenite/beta zeolite symbiotic molecular sieve catalyst prepared by the method can be used in the reaction of naphtha catalytic pyrolysis to prepare propylene.
Description
Technical field
The present invention relates to a kind of binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method.
Background technology
Molecular sieve has good shape selective catalysis performance and absorption property owing to have evenly regular pore passage structure, bigger specific area and higher thermally-stabilised row, is applied in field of petrochemical industry widely.Because molecular sieve powder self intensity is lower, be prone to disperse to run off, can't directly be applied in use in the industry; Therefore in use need add the binding agent moulding and gain in strength, in the catalyst after the moulding, because binding agent parcel molecular sieve; Caused the effective rate of utilization of molecular sieve to descend, the duct of the molecular sieve of part is blocked, causes the specific area of catalyst lower; Activity is also lower, and again because binding agent is no regular pore passage structure, reaction raw materials and product are in catalyst diffusion difficulty; Carbon deposit has certain influence to life of catalyst easily.Be converted into the active principle molecular sieve to the binding agent in the catalyst and then can overcome above problem, improve activity of such catalysts and diffusion.
The binder free catalyst is exactly the active principle that changes into the binding agent that is added in the molecular sieve catalyst forming process in molecular sieve, makes not contain the binding agent composition in the whole catalyst, keeps the good intensity of catalyst simultaneously.Be converted into the molecular sieve composition fully owing to binding agent in the binder free catalyst; So just improved the content of molecular sieve in the per volume of catalyst; Make activity of such catalysts higher, treating capacity is bigger, simultaneously owing to no longer include binding agent in the catalyst; Solved binding agent parcel molecular sieve and reduced the effective rate of utilization of molecular sieve and the problem that binding agent stops up molecular sieve pore passage, the effective rate of utilization of molecular sieve and carbon accumulation resisting ability are improved greatly.General Adhesive-free Molecular Sieve catalyst refers in the catalyst weight of binder content smaller or equal to 5%.
General coexisting molecular sieve is to prepare through the synthetic method of hydro-thermal, is Powdered, and no intensity is prone to run off, and can not directly use, and need add binding agent when industry or laboratory applications and carry out extrusion or spray shaping.In the general molecular sieve catalyst forming process, the weight that add binding agent is no less than 40% of total catalyst weight, though the moulding rear catalyst has had intensity, the effective rate of utilization of catalyst reduces, active and diffusion variation.
At present the binder free catalyst of report has the adhesiveless ZSM-5 molecular sieve, is to make through gas phase conversion at the presoma that preformed catalyst adds ZSM-5.
Chinese patent 200510028782 has reported that the present invention of small crystal grain without bonding agent modenite prepare zeolite method is a primary raw material through adopting with diatomite or white carbon; Add the crystal seed directed agents; And with Ludox or sodium metasilicate as the binding agent moulding; Handle the technical scheme that is converted into integrated microcrystal mordenites with organic amine mutually with the water vapour gas-solid then; Mainly solve the zeolite powder and in practical application, have the difficult weakness that reclaims, is prone to inactivation and gathering, and the adding binding agent can cause that effective surface area reduces the problem that influences with diffusion restriction in the forming process.
Chinese patent 200510029462 has been reported the preparation method of ZSM-type molecular sieve without binding agent.Through adopting content is the mixture that the former powder of 5～50 weight % binding agent silica and ZSM type molecule forms; In the aqueous solution that contains halogenation organic amine and alkyl diamine or steam; Be converted into the technical scheme of integrated ZSM type molecular sieve through hydrothermal treatment consists, mainly solved and add binding agent in the molecular sieve catalyst forming process and can cause that effective surface area reduces the problem with the diffusion restriction influence.
Composite molecular screen, coexisting molecular sieve or the mixed crystal molecular sieve of existing report all need be synthetic synthetic back of molecular sieve or adding crystal seed directed agents hydro-thermal, and building-up process is very complicated comparatively.Synthesizing flokite/beta zeolite coexisting the molecular sieve of report all is to be prepared from through the synthetic method of hydro-thermal at present.Add crystal seed or template in the building-up process, the complicated and pollution again of preparation method.
The method that directly prepares binder free mordenite/beta zeolite coexisting molecular sieve catalyst can be optimized preparation process, avoids preparing the process complicated problems, has tangible economic worth and social value.
At present, binder free composite molecular screen and preparation method thereof does not appear in the newspapers, and prepares the technology of binder free composite molecular screen and does not appear in the newspapers yet through adding single crystal seed.Therefore, binder free mordenite/beta zeolite coexisting molecular sieve catalyst does not have report as yet yet, is that crystal seed or directed agents prepare binder free mordenite/beta zeolite coexisting molecular sieve report is not more arranged through single molecular sieve.
Summary of the invention
Technical problem to be solved by this invention is that the mordenite/beta zeolite coexisting molecular sieve of prior art for preparing contains that binding agent, preparation process are complicated, cost is higher, the relatively poor and lower problem of mechanical impurity activity that contains the modenite and the β zeolite of binding agent of activity mordenite/beta zeolite coexisting molecular sieve intensity lower, that do not contain binding agent when containing binding agent in the mordenite/beta zeolite coexisting molecular sieve catalyst, and a kind of new method for preparing binder free mordenite/beta zeolite coexisting molecular sieve catalyst is provided.This method has that the preparation process is simple, and cost is lower, environmental protection, and it is higher to have catalytic activity with the catalyst of this method preparation in addition, simultaneously also advantage of higher of mechanical strength.
For addressing the above problem, the technical scheme that the present invention adopts is following: a kind of binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method may further comprise the steps:
A) catalyst weight meter; After the compound of the β zeolite 10～80%, 0.2～20% alkaline matter, 0.5～20% aluminium and 10～80% the silica mixed-forming drying; Obtain preformed catalyst precursor mixture I, wherein among the mixture I compound weight content of aluminium less than the weight content of silica;
B) thing I places to put into and contains at least a template steam that is selected from ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, carries out obtaining binder free mordenite/beta zeolite coexisting molecular sieve catalyst precarsor after crystallization is handled 10～240 hours at 120～200 ℃;
C) precursor 400～700 ℃ of following roastings 1～10 hour, obtains binder free mordenite/beta zeolite coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%, the SiO of β zeolite
2/ Al
2O
3Mol ratio is 20～100; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of I A or II A element; The compound of aluminium is selected from least a in the hydroxide of hydrous oxide or aluminium of oxide, aluminium of aluminium salt, aluminium.
SiO in the prepared mordenite/beta zeolite coexisting molecular sieve in the technique scheme
2/ Al
2O
3Preferable range is 20～120; I A major element preferred version is selected from least a in sodium or the potassium, and II A element preferred version is selected from least a in magnesium or the calcium; The salt of weak acid preferred version is selected from least a in carbonate, oxalates or the citrate; In the catalyst weight behind the shaping and roasting, the compound amount preferable range of aluminium is 1～10%; The consumption preferable range of β zeolite is 20～70%; The consumption preferable range of alkaline matter is 1～10%; The consumption preferable range of silica is 15～70%; The consumption preferable range of organic amine is 10～100%; The crystallization temperature preferable range is 140～180 ℃, and the crystallization time preferable range is 20～100 hours; The SiO of mordenite/beta zeolite coexisting molecular sieve
2/ Al
2O
3The mol ratio preferable range is 20～60, and wherein weight of binder content preferable range is 0～5%, and more preferably scope is 0.1～2%; The weight ratio preferable range of modenite and β zeolite is 0.5～80: 1 in the mordenite/beta zeolite coexisting molecular sieve, the crush strength preferable range of the binder free catalyst that makes be 60～150 newton/.
It is strip solid cylindrical, that diameter is 0.5～2mm that shape after the catalyst precarsor mixture I extrusion is generally tangent plane, is broken into every grain length degree after the drying and is 5 millimeters short cylindrical shape catalyst bar, is convenient to change brilliant and handles and examination.Catalyst mechanical strength among the present invention is calculated by this shape measure.Catalyst precarsor mixture I also can make cellular as required, clover shape, hollow tubular or shape such as spherical, and its strength criterion is meter in addition.
In the characterization method of binder free catalyst, with the contained thing of XRD test mutually and the content of each thing phase, change the pattern of molecular sieve of situation and the generation of crystalline substance with the scanning electron microscopic observation binding agent.Change brilliant back binder content confirm through the XRD thing mutually quantitatively and in the stereoscan photograph content of binding agent confirm.The catalyst silica alumina ratio is confirmed with chemico-analytic method.The strength test method of catalyst is the crushing strength of the catalyst after test roasting on the pressure testing machine; Every of the catalyst of surveying is of a size of 1.5 millimeters of diameters; 5 millimeters of length; Be disposed across on the testing machine, suffered maximum pressure when measuring catalyst breakage is got its mean value after testing 10 catalyst crushing strengths.
The present invention puts into the template steam of specific suitable modenite growth through in preformed catalyst, adding single crystal seed β zeolite, and control is suitable for the alkaline environment and the material proportion of modenite and β zeolite growth simultaneously; Make binding agent under the inducing of β zeolite seed crystal; β zeolite active ingredient can be changed into, in the control environment of template steam and alkalescence, also the modenite crystal seed can be induced in the binding agent simultaneously; And can nucleating growth; Therefore binding agent can be transformed into the coexisting molecular sieve active principle through the method for gas phase conversion, obtains binder free type mordenite/beta zeolite coexisting molecular sieve catalyst, reaches the purpose of simple environmental protection.The content of binding agent can reach below 1% in the binder free type mordenite/beta zeolite coexisting molecular sieve catalyst that makes; Even do not contain binding agent; All the mordenite/beta zeolite coexisting molecular sieve in the catalyst; Improve the content of coexisting molecular sieve in the per volume of catalyst like this, improved activity of such catalysts.Owing to change staggered growth between the binder free coexisting molecular sieve thing phase that obtains behind the crystalline substance,,, can reach more than 180 newton so the intensity of catalyst is also higher in conjunction with tightr.The catalyst that makes can be used in the reaction of naphtha catalytic pyrolysis preparing propylene, and the diene weight yield of ethylene, propylene can reach more than 54.5%, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of the binder free mordenite/beta zeolite coexisting molecular sieve catalyst of embodiment 1 preparation.
Fig. 2 is the ESEM picture of the binder free mordenite/beta zeolite coexisting molecular sieve catalyst of embodiment 1 preparation.
Through specific embodiment the present invention being done a nearly step below sets forth.
The specific embodiment
[embodiment 1]
Get SiO
2/ Al
2O
3Mol ratio is 40 β zeolite 60 grams, and adding quality percentage composition is 40% Ludox 40 grams and aluminum sulfate 16 grams, after the mixing and stirring; 10 milliliters of sodium hydroxide solutions that add 1 mol again, mixing and stirring, the moulding of agent bar then; Preformed catalyst is 80 ℃ of oven dry 3 hours, put into then the inner bag bottom moisture with the hexamethylene diamine mass ratio be 200 milliliters autoclave of 1: 1 mixed solution 40 gram, catalyst does not contact with liquid water; Put into baking oven after the autoclave sealing, 180 ℃ of crystallization were taken out after 60 hours, washed then 2 times; Put into 120 ℃ in baking oven oven dry 3 hours, putting into the 400 ℃ of roastings 2 hours that heat up of Muffle furnace internal program, 550 ℃ of roastings 3 hours; Make binder free mordenite/beta zeolite coexisting molecular sieve catalyst; Wherein the weight percentage of modenite is 35.7%, and the β zeolite content is 63.3%, and the withstand voltage broken intensity of detecting catalyst sample is 160 newton.。The XRD figure spectrum of the catalyst that makes is as shown in Figure 1, and it is shown as the thing phase of mordenite/beta zeolite.The ESEM picture of the catalyst that makes is as shown in Figure 2, and it is shown as the mixture of ball-type modenite crystal grain and β zeolite grain, and the binder content of unformed state is 1%.
[embodiment 2～6]
According to the method for embodiment 1, get SiO respectively
2/ Al
2O
3Mol ratio be 20,40,60,80 and 100 β zeolite as crystal seed, other condition is constant, it is as shown in table 1 that raw material is formed proportioning, the binder free catalyst that makes is as shown in table 2.
[embodiment 7～13]
Method according to embodiment 1; Other condition is constant, in forming process, adds soluble starch, sesbania powder or methylcellulose, and it is as shown in table 1 that raw material is formed proportioning; Mixing and stirring; Extruded moulding is processed binder free mordenite/beta zeolite coexisting molecular sieve catalyst by the method for embodiment 1 again, and the result is as shown in table 2.
[embodiment 14]
Method according to embodiment 1 makes binder free mordenite/beta zeolite coexisting molecular sieve catalyst; Use concentration is 5% ammonium nitrate solution; It in the solid-to-liquid ratio of catalyst and ammonium nitrate solution 1: 10 ratio; 90 ℃ of exchanges three times, 550 ℃ of roastings made the binder free mordenite/beta zeolite coexisting molecular sieve catalyst of Hydrogen after 3 hours then.The component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material (the raw material physical index is seen table 3), the examination activity of such catalysts, using diameter is 12 millimeters fixed bed reactors normal pressure examination down, range of reaction temperature is 650 ℃, reaction pressure is 0.02MPa, mass space velocity is 1 hour
-1, water/feedstock oil mass ratio is 1: 1, the reaction half an hour after, products distribution is seen table 4, feed stock conversion is 94.5%, obtaining the ethene mass yield is 29.5%, the propylene mass yield is 24%, diene quality total recovery is 54.5%.
Table 2
| Embodiment | Gained molecular sieve SiO 2/Al 2O 3 | Modenite content (weight %) | β zeolite content (weight %) | Binder content (weight %) | Catalyst strength (newton /) |
| |
60 | 23.0 | 76.0 | 1.0 | 120 |
| Embodiment 3 | 20 | 34.5 | 64.0 | 1.5 | 160 |
| Embodiment 4 | 90 | 45.4 | 53.6 | 1.0 | 150 |
| Embodiment 5 | 70 | 46.5 | 52.0 | 1.5 | 130 |
| Embodiment 6 | 50 | 1.5 | 98.5 | 0 | 190 |
| Embodiment 7 | 90 | 8.4 | 90.4 | 1.2 | 120 |
| Embodiment 8 | 100 | 45.4 | 53.6 | 1.0 | 155 |
| Embodiment 9 | 50 | 31.6 | 63.4 | 5 | 50 |
| |
80 | 81.4 | 15.5 | 3.1 | 80 |
| Embodiment 11 | 30 | 85.3 | 14.5 | 0.2 | 200 |
| Embodiment 12 | 60 | 56.5 | 43.0 | 0.5 | 185 |
| Embodiment 13 | 120 | 88.8 | 10.3 | 0.9 | 120 |
Table 3 light oil raw material index
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.2 |
| Cycloalkane % (weight %) | 28.4 |
| Alkene % (weight %) | 0.2 |
| Aromatic hydrocarbons % (weight %) | 6.2 |
[embodiment 15]
Get the binder free type mordenite/beta zeolite that obtains among the embodiment 1, process hydrogen type catalyst, get 100 grams by the method for embodiment 14; Using concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.5 mol flooded modification 4 hours at 95 ℃; Take out sample 120 ℃ of oven dry 3 hours then,, obtain the binder free type mordenite/beta zeolite coexisting molecular sieve catalyst of phosphorus modification again 650 ℃ of roastings 3 hours; Method according to embodiment 14 is checked and rated, and the result sees table 5.
[embodiment 16]
Get binder free type mordenite/beta zeolite coexisting molecular sieve catalyst 100 grams of the phosphorus modification that obtains among the embodiment 15; Using concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.2 mol flooded modification 4 hours at 95 ℃; Take out sample 120 ℃ of oven dry 3 hours then,, obtain the binder free type ZSM-5/ beta zeolite coexisting molecular sieve catalyst of lanthanum and phosphorus modification again 650 ℃ of roastings 3 hours; Method according to embodiment 14 is checked and rated, and the result sees table 5.
[comparative example 1]
Preparing silica alumina ratio by the method for Chinese patent CN1647856A is 40 mordenite/beta zeolite mixed crystal molecular sieve; Method by embodiment 14 is processed hydrogen type molecular sieve; Then mixed crystal molecular sieve direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 2]
Preparing silica alumina ratio by the method for Chinese patent CN1647856A is 40 mordenite/beta zeolite mixed crystal molecular sieve; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the mordenite/beta zeolite mixed crystal molecular sieve catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 3]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 modenite; Method by embodiment 14 is processed hydrogen type molecular sieve; Then the modenite direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 4]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 14 is processed hydrogen type molecular sieve; Then β zeolite direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
[comparative example 5]
The silica alumina ratio that Oil of Shanghai Petrochemical Company research institute produces is 40 modenite; Method by embodiment 14 is processed hydrogen type molecular sieve, processes hydrogen type molecular sieve by the method for embodiment 14, and then according to the method extruded moulding of embodiment 1; Obtain containing the ZSM-5 molecular sieve catalyst of binding agent; Put into fixed bed reactors, press the method examination of embodiment 14, the result sees table 5.
[comparative example 6]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 14 is processed hydrogen type molecular sieve, processes hydrogen type molecular sieve by the method for embodiment 14 then, and then according to the method extruded moulding of embodiment 1; Obtain containing the beta zeolite coexisting molecular sieve catalyst of binding agent; Put into fixed bed reactors, press the method examination of embodiment 14, the result sees table 5.
[comparative example 7]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 modenite, and silica alumina ratio is 40 β zeolite, is mixed into mechanical impurity at 1: 1 according to weight ratio; Method by embodiment 14 is processed hydrogen type molecular sieve; And then, obtain containing the modenite of binding agent and the catalyst of β zeolite mechanical impurity according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 14, the result sees table 5.
Table 4
| Product is formed | Product weight yield (%) |
| Methane | 4.5 |
| Ethane | 6.8 |
| Ethene | 29.5 |
| Propane | 6.3 |
| Propylene | 24.0 |
| Butane | 8.8 |
| Butylene | 7.4 |
| Carbon five above cuts | 8.1 |
| Other | 4.6 |
Table 5
| Embodiment | Catalyst strength (newton /) | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) | React 0.5 hour conversion ratio (%) |
| Embodiment 15 | 143 | 30 | 25.5 | 55.5 | 98 |
| Embodiment 16 | 138 | 29 | 25 | 54 | 97 |
| Comparative example 1 | 36 | 24 | 21 | 45 | 88 |
| Comparative example 2 | 84 | 23 | 20 | 43 | 83 |
| Comparative example 3 | 35 | 22 | 19 | 39 | 76 |
| Comparative example 4 | 30 | 21 | 20 | 41 | 75 |
| Comparative example 5 | 76 | 20 | 18 | 38 | 73 |
| Comparative example 6 | 60 | 21 | 21 | 42 | 78 |
| Comparative example 7 | 65 | 25 | 21 | 47 | 86 |
Claims (4)
1. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method may further comprise the steps:
A) the catalyst weight meter after the molded roasting; After the compound of the β zeolite 10～80%, 0.2～20% alkaline matter, 0.5～20% aluminium and 10～80% silica mixing, moulding, the drying; Obtain preformed catalyst precursor mixture I, wherein among the preformed catalyst precursor mixture I compound weight content of aluminium less than the weight content of silica;
B) preformed catalyst precursor mixture I places to put into and contains at least a template steam that is selected from ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, carries out obtaining binder free mordenite/beta zeolite coexisting molecular sieve catalyst precarsor after crystallization is handled 10～240 hours at 120～200 ℃;
C) binder free mordenite/beta zeolite coexisting molecular sieve catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains binder free mordenite/beta zeolite coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%, the SiO of β zeolite
2/ Al
2O
3Mol ratio is 20～100; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of I A family or II A family element; The compound of aluminium is selected from least a in the hydroxide of hydrous oxide or aluminium of oxide, aluminium of aluminium salt, aluminium.
2. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method according to claim 1 is characterized in that I A family element is selected from least a in sodium or the potassium, and II A family element is selected from least a in magnesium or the calcium; Salt of weak acid is selected from least a in carbonate, oxalates or the citrate.
3. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method according to claim 1 is characterized in that crystallization temperature is 140-180 ℃, and crystallization time is 20～100 hours.
4. binder free mordenite/beta zeolite coexisting molecular sieve Preparation of catalysts method according to claim 1 is characterized in that the SiO of prepared mordenite/beta zeolite coexisting molecular sieve catalyst
2/ Al
2O
3Mol ratio is 20～120, and wherein weight of binder content is 0; The weight ratio of modenite and β zeolite is 0.5-80 in the mordenite/beta zeolite coexisting molecular sieve: 1, the catalyst crush strength behind the shaping and roasting be 60-150 newton/.
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|---|---|---|---|---|
| CN1648046A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Processfor preparing mordenite and beta zeolite mixed crystal material |
| CN1915820A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain without bonding agent |
| CN100998950A (en) * | 2006-01-11 | 2007-07-18 | 中国石油化工股份有限公司 | Catalyst used for heavy arene lightenation and alkyl transfer and its preparation method |
| CN101491772A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Catalyst for naphtha catalytic cracking |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648046A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Processfor preparing mordenite and beta zeolite mixed crystal material |
| CN1915820A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain without bonding agent |
| CN100998950A (en) * | 2006-01-11 | 2007-07-18 | 中国石油化工股份有限公司 | Catalyst used for heavy arene lightenation and alkyl transfer and its preparation method |
| CN101491772A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Catalyst for naphtha catalytic cracking |
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| Title |
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| JP特开2007-252989A 2007.10.04 |
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